CN103346321A - Preparation method of carbon-doped lithium titanate for lithium-ion battery negative material - Google Patents
Preparation method of carbon-doped lithium titanate for lithium-ion battery negative material Download PDFInfo
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- CN103346321A CN103346321A CN2013102540989A CN201310254098A CN103346321A CN 103346321 A CN103346321 A CN 103346321A CN 2013102540989 A CN2013102540989 A CN 2013102540989A CN 201310254098 A CN201310254098 A CN 201310254098A CN 103346321 A CN103346321 A CN 103346321A
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Abstract
The invention relates to a preparation method of carbon-doped lithium titanate for a lithium-ion battery negative material, which solves the technical problem in the prior art by adopting carbon-doped lithium titanate synthesized through a solid synthesis method as a lithium-ion battery negative material, the magnification performance of the battery is poor due to the rapid attenuation of the capacity in large-current charging-discharging. The preparation method is characterized in that titanium isopropoxide is adopted as a titanium source, the titanium source is compounded with oxidized graphite and then is mixed with a lithium source, the titanium isopropoxide is hydrolyzed to obtain the mixture of titanium dioxide and oxidized graphite, the conductivity of the material is improved, the flaky structure of the oxidized graphite provides a supporting skeleton for the subsequent lithiation process, so that the lithium titanate material has a flaky appearance. When the carbon-doped lithium titanate material with the flaky appearance is used as the lithium-ion battery negative material, the contact area between the electrolyte and active substances can be increased, an effect for rapidly transmitting lithium ions can be realized, and the obtained battery is excellent in cycling stability and magnification performance.
Description
Technical field
The present invention relates to a kind of preparation method of lithium ion battery negative material carbon doped lithium titanate, belong to electrochemical energy material technology field.
Background technology
Because the restriction of lattice structure, the conductivity of lithium titanate is relatively poor, has limited the performance of its large current discharging capability, but can change this characteristic by ion doping.Have at present and utilize material with carbon element to mix to improve lithium titanate conductivity.Lithium titanate is carried out the doping of material with carbon element, not only can improve the conductivity of material, make it to have high rate capability preferably, and can also stop the particle of material in the calcination process phenomenon of growing up, utilize the final pattern of the special appearance control lithium titanate of material with carbon element, realize the abundant infiltration of electrolyte and the quick transmission of electronics.But existing carbon doped lithium titanate adopts solid-phase synthesis synthetic more, and synthetic material particle size is big, particle is easy to reunite, electron conduction is poor.Used as lithium ion battery negative material, capacity attenuation causes the battery high rate performance relatively poor rapidly when high current charge-discharge.
Summary of the invention
The present invention will solve the carbon doped lithium titanate that solid-phase synthesis synthesizes in the prior art and be used as lithium ion battery negative material, capacity attenuation causes the relatively poor technical problem of battery high rate performance rapidly when high current charge-discharge, a kind of preparation method of lithium ion battery negative material carbon doped lithium titanate is provided, the carbon doped lithium titanate that makes can improve cyclical stability and the high rate performance of battery as lithium ion battery negative material.
In order to solve the problems of the technologies described above, technical scheme of the present invention is specific as follows:
A kind of preparation method of lithium ion battery negative material carbon doped lithium titanate, this preparation method may further comprise the steps:
(1) is dispersed in the 20mL deionized water 22mg graphite oxide (GO) is ultrasonic, to wherein dripping isopropyl titanate, stirred 2-6 hour, obtain TiO
2/ GO compound;
(2) with lithium hydroxide solution and above-mentioned TiO
2/ GO compound mixes;
(3) mixed solution that step (2) is obtained is transferred in the reactor, carries out hydro-thermal reaction, and reaction temperature is 140-200 ℃, and the reaction time is 24-30 hour, obtains the reactant presoma;
(4) with above-mentioned reactant presoma with deionized water and ethanol centrifuge washing, after the oven dry, in air, in 300-400 ℃ of calcining 20-30 minute down, be cooled to after the room temperature at N
2Calcined 2-4 hour down in 600-700 ℃ in the atmosphere, obtain carbon doped titanic acid lithium material.
In technique scheme, the dripping quantity of isopropyl titanate is 1-3mL in the step (1).
In technique scheme, the concentration of lithium hydroxide solution is 0.4M in the step (2).
In technique scheme, step is carried out twice calcining with the reactant presoma described in (4), and its heating rate all is controlled to be 3-5 ℃/minute.
In technique scheme, with the oven dry of reactant presoma, its bake out temperature is 60-80 ℃ described in the step (4).
The preparation method's of lithium ion battery negative material carbon doped lithium titanate provided by the invention beneficial effect is:
The present invention adopts liquid phase hydrothermal synthesis of carbon doped lithium titanate presoma, then presoma is heat-treated, adopt two step calcination methods can effectively suppress the increase of lithium titanate crystal, simultaneous oxidation graphite is reduced to graphite, after compound with lithium titanate, be conducive to improve electron conduction, the carbon that is reduced is still keeping the sheet pattern, and the carbon doped lithium titanate composite material of Xing Chenging also has sheet pattern (seeing accompanying drawing 1) like this.The carbon doped titanic acid lithium material of this pattern is used for lithium ion battery negative material, can increase the contact area of electrolyte and active material, has reached the lithium ion effect of transmission fast, the battery cyclical stability that obtains and high rate performance excellence.The carbon doped titanic acid lithium material that embodiment two preparations has been described as accompanying drawing 2 under 1C, charge and discharge cycles 100 times, capacity is decayed hardly.Accompanying drawing 3 has illustrated the carbon doped titanic acid lithium material of embodiment three preparations under 5C, and discharge capacity can be up to 155mAh/g, and circulates 100 times, and capacity attenuation is small.Accompanying drawing 4 has illustrated the carbon doped titanic acid lithium material of embodiment four preparations under the 10C current density, and capacity still can remain on more than the 110mAh/g, and when the 1C of back, capacity can be returned to 150mAh/g.
Description of drawings
Fig. 1 is the SEM figure of the carbon doped titanic acid lithium material of the embodiment of the invention one preparation.
Fig. 2 is the cycle performance figure of carbon doped titanic acid lithium material under 1C of the embodiment of the invention two preparations.
Fig. 3 is the cycle performance figure of carbon doped titanic acid lithium material under 5C of the embodiment of the invention three preparations.
Fig. 4 is the high rate performance figure of carbon doped titanic acid lithium material under different current densities of the embodiment of the invention four preparations.
Embodiment
Preparation method's concrete steps of a kind of lithium ion battery negative material carbon doped lithium titanate provided by the invention are:
(1) is dispersed in the 20mL deionized water 22mg graphite oxide (GO) is ultrasonic, to wherein slowly dripping the 1-3mL isopropyl titanate, stirred 2-6 hour, obtain TiO
2/ GO compound;
(2) with concentration be 0.4M lithium hydroxide solution and above-mentioned TiO
2/ GO compound mixes;
(3) mixed solution that step (2) is obtained is transferred in the reactor, carries out hydro-thermal reaction, and reaction temperature is 140-200 ℃, and the reaction time is 24-30 hour, obtains the reactant presoma;
(4) with above-mentioned reactant presoma with deionized water and ethanol centrifuge washing, put into vacuum drying chamber in 60-80 ℃ down after the oven dry, in air, in 300-400 ℃ of calcining 20-30 minute down, be cooled to after the room temperature at N
2Calcined 2-4 hour down in 600-700 ℃ in the atmosphere, heating rate all is controlled to be 3-5 ℃/minute, obtains carbon doped titanic acid lithium material.
Embodiment one
At first be dispersed in the 20mL deionized water 22mg graphite oxide (GO) is ultrasonic, to wherein slowly dripping the 1mL isopropyl titanate, strong agitation 2 hours forms TiO
2/ GO compound, again the 0.4M lithium hydroxide solution 20mL that configures is mixed with above-mentioned compound, then above-mentioned mixed solution is transferred in the reactor, carry out hydro-thermal reaction, temperature is controlled to be 140 ℃, 24 hours time, after hydro-thermal reaction finishes the reactant presoma usefulness deionized water and the ethanol that obtain are distinguished centrifuge washing three times, oven dry back 300 ℃ of calcinings 20 minutes in air in 60 ℃ of vacuum drying ovens, be cooled to after the room temperature in nitrogen 600 ℃ of calcinings 2 hours, heating rate is 3 ℃/minute, finally obtains carbon doped titanic acid lithium powder.Accompanying drawing 1 is the SEM figure of the carbon doped titanic acid lithium material of present embodiment preparation, this figure illustrates that carbon doped titanic acid lithium material has the sheet pattern, the carbon doped titanic acid lithium material of this pattern is as lithium ion battery negative material, can increase the contact area of electrolyte and active material, reach the lithium ion effect of transmission fast.
Embodiment two
At first be dispersed in the 20mL deionized water 22mg graphite oxide (GO) is ultrasonic, to wherein slowly dripping the 3mL isopropyl titanate, strong agitation 6 hours forms TiO
2/ GO compound, again the 0.4M lithium hydroxide solution 20mL that configures is mixed with above-mentioned compound, then above-mentioned mixed solution is transferred in the reactor, carry out hydro-thermal reaction, temperature is controlled to be 200 ℃, 30 hours time, after hydro-thermal reaction finishes the reactant presoma usefulness deionized water and the ethanol that obtain are distinguished centrifuge washing three times, oven dry back 400 ℃ of calcinings 30 minutes in air in 80 ℃ of vacuum drying ovens, be cooled to after the room temperature in nitrogen 700 ℃ of calcinings 4 hours, heating rate is 5 ℃/minute, finally obtains carbon doped titanic acid lithium powder.Accompanying drawing 2 is the cycle performance figure of carbon doped titanic acid lithium material under 1C of present embodiment preparation, and this figure has illustrated the carbon doped titanic acid lithium material of preparation under 1C, charge and discharge cycles 100 times, and capacity is decayed hardly.
Embodiment three
At first be dispersed in the 20mL deionized water 22mg graphite oxide (GO) is ultrasonic, to wherein slowly dripping the 2mL isopropyl titanate, strong agitation 4 hours forms TiO
2/ GO compound, again the 0.4M lithium hydroxide solution 20mL that configures is mixed with above-mentioned compound, then above-mentioned mixed solution is transferred in the reactor, carry out hydro-thermal reaction, temperature is controlled to be 180 ℃, 28 hours time, after hydro-thermal reaction finishes the reactant presoma usefulness deionized water and the ethanol that obtain are distinguished centrifuge washing three times, oven dry back 350 ℃ of calcinings 30 minutes in air in 60 ℃ of vacuum drying ovens, be cooled to after the room temperature in nitrogen 600 ℃ of calcinings 3 hours, heating rate is 5 ℃/minute, finally obtains carbon doped titanic acid lithium powder.Accompanying drawing 3 is the cycle performance figure of carbon doped titanic acid lithium material under 5C of present embodiment preparation, and this figure has illustrated the carbon doped titanic acid lithium material of preparation under 5C, and discharge capacity can be up to 155mAh/g, and circulates 100 times, and capacity attenuation is small.
Embodiment four
At first be dispersed in the 20mL deionized water 22mg graphite oxide (GO) is ultrasonic, to wherein slowly dripping the 3mL isopropyl titanate, strong agitation 2 hours forms TiO
2/ GO compound, again the 0.4M lithium hydroxide solution 20mL that configures is mixed with above-mentioned compound, then above-mentioned mixed solution is transferred in the reactor, carry out hydro-thermal reaction, temperature is controlled to be 140 ℃, 30 hours time, after hydro-thermal reaction finishes the presoma usefulness deionized water and the ethanol that obtain are distinguished centrifuge washing three times, oven dry back 350 ℃ of calcinings 25 minutes in air in 60 ℃ of vacuum drying ovens, be cooled to after the room temperature in nitrogen 600 ℃ of calcinings 3 hours, heating rate is 4 ℃/minute, finally obtains carbon doped titanic acid lithium powder.Fig. 4 is the high rate performance figure of carbon doped titanic acid lithium material under different current densities of present embodiment preparation, this figure has illustrated that the carbon doped titanic acid lithium material of preparation is under the 10C current density, capacity still can remain on more than the 110mAh/g, and when the 1C of back, capacity can be returned to 150mAh/g.
Obviously, above-described embodiment only is for example clearly is described, and is not the restriction to execution mode.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here need not also can't give all execution modes exhaustive.And the apparent variation of being extended out thus or change still are among the protection range of the invention.
Claims (5)
1. the preparation method of a lithium ion battery negative material carbon doped lithium titanate is characterized in that, this preparation method may further comprise the steps:
(1) is dispersed in the 20mL deionized water 22mg graphite oxide (GO) is ultrasonic, to wherein dripping isopropyl titanate, stirred 2-6 hour, obtain TiO
2/ GO compound;
(2) with lithium hydroxide solution and above-mentioned TiO
2/ GO compound mixes;
(3) mixed solution that step (2) is obtained is transferred in the reactor, carries out hydro-thermal reaction, and reaction temperature is 140-200 ℃, and the reaction time is 24-30 hour, obtains the reactant presoma;
(4) with above-mentioned reactant presoma with deionized water and ethanol centrifuge washing, after the oven dry, in air, in 300-400 ℃ of calcining 20-30 minute down, be cooled to after the room temperature at N
2Calcined 2-4 hour down in 600-700 ℃ in the atmosphere, obtain carbon doped titanic acid lithium material.
2. the preparation method of lithium ion battery negative material carbon doped lithium titanate according to claim 1 is characterized in that, the dripping quantity of isopropyl titanate is 1-3mL in the step (1).
3. the preparation method of lithium ion battery negative material carbon doped lithium titanate according to claim 1 is characterized in that, the concentration of lithium hydroxide solution is 0.4M in the step (2).
4. the preparation method of lithium ion battery negative material carbon doped lithium titanate according to claim 1 is characterized in that, step is carried out twice calcining with the reactant presoma described in (4), and its heating rate all is controlled to be 3-5 ℃/minute.
5. the preparation method of lithium ion battery negative material carbon doped lithium titanate according to claim 1 is characterized in that, with the oven dry of reactant presoma, its bake out temperature is 60-80 ℃ described in the step (4).
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105470483A (en) * | 2015-12-04 | 2016-04-06 | 齐鲁工业大学 | Preparation method of anode material N-doped carbon-coated cobaltous oxide nanotube for lithium-ion battery |
| CN108630441A (en) * | 2018-04-28 | 2018-10-09 | 南京林业大学 | A kind of biomass graded porous carbon supporting nanostructures sodium titanate and preparation method thereof |
-
2013
- 2013-06-24 CN CN2013102540989A patent/CN103346321A/en active Pending
Non-Patent Citations (2)
| Title |
|---|
| LAIFA SHEN ET.AL: "Insitu synthesis of high-loading Li4Ti5O12–graphene hybrid nanostructures for high rate lithium ion batteries", 《（COMMUNICATION）NANOSCALE》 * |
| 宁峰: "钛酸锂制备工艺及其产气机理研究", 《中国优秀硕士学位论文全文数据库 工程科技II辑》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105470483A (en) * | 2015-12-04 | 2016-04-06 | 齐鲁工业大学 | Preparation method of anode material N-doped carbon-coated cobaltous oxide nanotube for lithium-ion battery |
| CN105470483B (en) * | 2015-12-04 | 2018-10-16 | 齐鲁工业大学 | A kind of preparation method of lithium ion battery negative material N- doping carbon coating cobaltous oxide nano-tube |
| CN108630441A (en) * | 2018-04-28 | 2018-10-09 | 南京林业大学 | A kind of biomass graded porous carbon supporting nanostructures sodium titanate and preparation method thereof |
| CN108630441B (en) * | 2018-04-28 | 2020-09-04 | 南京林业大学 | Biomass hierarchical porous carbon loaded nano-structure sodium titanate and preparation method thereof |
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Application publication date: 20131009 |